FI89772C - CHEMICAL REACTION FOR CHEMICAL REQUIREMENTS - Google Patents

Description

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Method and apparatus for performing controlled chemical reactions

The present invention generally relates to methods and apparatus for carrying out chemical reactions. More specifically, the invention relates to a process according to the preamble of claim 1 and an apparatus according to the preamble of claim 7 for carrying out chemical reactions, such as aqueous oxidation reactions.

The chemical structure of a substance changes under different conditions. These conditions may include the presence of a particular reactance, reactant concentration, temperature and pressure, and the nature of the reaction vessel. By closely monitoring the environmental conditions of a substance, the desired chemical reaction can be accomplished at a predetermined reaction rate to produce a particular product. Thus, the development of suitable economic reaction schemes is an important goal in chemical process technology.

Several oxidation reactions are performed in a liquid medium. One such reaction is aqueous phase oxidation, or "wet oxidation." Oxidation of the combustible material requires a sufficiently high temperature for ignition, thorough mixing to promote contact between the reactants, and sufficient time to perform wet oxidation. Wet oxidation of a combustible substance is an exothermic reaction that generates significant amounts of heat. In some processes, the heat released by this exothermic reaction is used to maintain the autogenous ignition temperature of the combustible materials. Thus, a self-sustaining wet oxidation process can be achieved.

Wet oxidation of combustible material has formed 35 important reactions in municipal waste treatment. Several f '·' ·> 2 different process systems have been proposed, most of which have had only limited success. One exception is the underground or "downhole" wet oxidation of municipal waste sludge. U.S. Patent No. 4,272,383 to McGrew, assigned to the assignee of this patent and incorporated herein by reference, discloses principles relating to a first known well-known vertical tube downhole reaction system for the wet oxidation of municipal waste. The waste treatment device includes a reaction vessel comprising a plurality of concentric conduits or tubes extending vertically into the ground to a depth of about one mile. This pipe combination forms an inflow channel through which the diluted municipal waste is sprayed as an inflow of waste, as well as an outflow channel. The sprayed waste is passed to a reaction vessel to form a hydrostatic column which causes considerable liquid pressure. The temperature of the inflowing waste stream can be increased by means of the heating device 20 as the flow flows into the reaction vessel. Compressed air is sprayed into the downstream effluent stream, preferably by the formation of Taylor-type gas bubbles.

At a depth of about 304.8 to 1828.8 meters (1000 to 6000 feet), a reaction zone is formed in which the wet oxidation of the waste becomes self-sustaining, provided, of course, that the concentration of reactants (combustible and oxygen) is sufficiently high. The temperature in the reaction zone is generally about 260 to 316 ° C (500 to 600 ° F). Boiling is prevented by the fluid pressure exerted by the hydrostatic column. The heat exchange jacket can be used to remove heat or generate heat in the reaction zone. The McGrew patent controls the ambient temperature. concentric inner tubes for pumping heated oil or other heat exchange fluid

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3 jacks to control the temperature of the reaction zone. This process is usually continuous, so that municipal waste and reaction products always pass through the reaction vessel. Thus, the flow rate of the liquid waste must be controlled together with the concentration of reactants in order to essentially completely oxidize the combustible materials in the reaction zone. The reaction products then pass through an outflow channel, which is usually a ring of concentric tubes. As will be described in more detail below, the flow pattern of the reactants in the flow through the reaction vessel will largely determine the success of the operation of the waste treatment system.

Only limited success has been achieved with known terrestrial systems for the wet oxidation of municipal waste. Thus, they have generally not been able to replace waste treatment systems such as clarification, water separation, drying, waste incineration, etc. Conventional terrestrial systems are inefficient due to their high energy requirements, inability to process waste quickly, and incomplete oxidation of waste materials. In addition, the construction, operation and maintenance of known terrestrial systems are expensive. In this connection, reference is made, for example, to U.S. Patent Nos. 2,665,249, Zimmerman and 2,932,613 to Huesler et al.

The suitability of an apparatus or method for carrying out a continuous wet oxidation reaction as described is determined in part by its flow pattern or pattern, including precipitation times for both vapor and liquid portions, and flow rate stability. Thus, it would be desirable to provide a method and apparatus in which wet oxidation or a similar reaction can be performed while allowing substantial mixing of the reactants 35 to facilitate mass transfer.

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It would also be desirable to provide a method and apparatus for wet oxidation in which the relative precipitation times for both the liquid and vapor portions complement the reaction process. In addition, it would be desirable to provide a method and apparatus for wet oxidation that provides a stable flow rate of reactants and products. The present invention provides a method and apparatus for achieving these and other objects.

The processing apparatus and method of the present invention can be used to perform chemical reactions with minimal initial capital cost, relatively high overall thermodynamic efficiency, excellent traction and durability, simple structures and operation, and minimal space required. In addition, the present invention provides a novel surface-based method and apparatus for promoting chemical reactions at high temperatures and pressures without the need for conventional large pressure vessels 20, the use of which requires constant mechanical agitation and considerable ground area. The present invention also solves the numerous environmental, energy overload, and maintenance problems associated with current terrestrial waste management practices.

The method according to the invention is characterized in that a) the first reagent is introduced into a long continuous thin-walled tubular coil under a predetermined pressure, the tubular coil being arranged horizontally in a vessel filled with a heat transfer medium in direct contact with the coil; c) the reagent feed and flow rates and relative volumes are adjusted under a predetermined pressure to provide a two-stage 5 '~ / plug and seal flow of reagents through the tubular coil, and d) the temperature of the fluid flow in the tubular coil is controlled. to increase the heat at a liquid flow temperature below a predetermined temperature and to remove heat at a predetermined liquid flow temperature above the temperature to initiate a chemical reaction in the liquid stream, resulting in heated liquid and reaction products. The invention also relates to a device characterized in that a long continuous thin-walled tubular coil arranged horizontally in the vessel, into which the liquid flow comprising the reagents is directed at a selected flow rate, directly into the coil to control the temperature of the liquid in the helix to increase heat at a liquid flow temperature below a predetermined temperature and to remove heat at a liquid flow temperature higher than a predetermined temperature to initiate a chemical reaction in the liquid flow from the liquid stream to the heated liquid and reaction products;

The reaction system of the present invention for carrying out accelerated chemical reactions comprises a long tubular coil as a basic component. The incoming waste vapor, i.e. the first reactance 30, is directed to pass through this tubular coil, whereby a second reactance is added to this waste stream. The reaction system can be used for wet oxidation of an inflowing waste stream comprising dilute organic waste by spraying air or pure oxygen into the waste stream.

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In one embodiment of the invention, said tubular coil is placed in a tank which is divided by means of partitions into a series of successive compartments filled with heat exchange fluid. The liquid-5 in each compartment can be adjusted to different levels with respect to the tubular coil immersed in the liquid. In addition, the heat exchange fluid can be heated to an initial temperature that allows a chemical reaction to occur in the waste stream within the tubular coil. Alternatively, heat can be removed from the heat exchange fluid after the reaction in the tubular coil has become autogenous.

For example, when treating dilute organic waste in the reaction system of the present invention, the inflowing liquid waste is pumped into a tubular coil at a pressure of about 70.3 to 140.6 kg / cm 2 (1000 to 2000 psi) with the addition of a gas such as air or oxygen. The flow rates of gaseous and liquid waste are adjusted to cause a two-stage waste flow, shut-off or plug flow through the tubular coil, resulting in thorough mixing of the reactances. The reactants are heated inside the coil to a temperature that causes oxidation of the waste stream, which is generally 149 to 316 ° C (300 to 600 ° F). Thus, the reaction in the coil takes place under the combined conditions of high pressure, high temperature and two-stage shut-off flow of the waste stream. However, the reaction system of this invention is particularly suitable for the disposal of toxic and industrial wastes such as chlorinated hydrocarbons, cyanides, organic and inorganic phenols, polyaromatic mixtures, etc. However, it will be appreciated that the reaction system of this invention may also be used to treat various chemicals and solids dissolved in a liquid when chemical oxidation-35 reduction is not the primary goal. The recommended temperature and pressure thus depend on the intended reaction.

7 '·' .- This system advantageously uses a thin-walled reaction vessel, i.e. a tubular coil which, due to its helical length, allows the necessary precipitation time for the reactants in the reaction zone 5, allowing the desired amount of oxidation to take place. The high temperature and pressure required for the reaction are generated in this thin-walled tube, which is exceptional, as these types of reactions are normally performed in thick-walled pressure vessels. As described in more detail below, the tube may normally have a diameter of about 5.08 cm (two inches) and a wall thickness of about 0.63 cm (1/4 inch), with the reaction occurring at about 316 ° C (600 ° F). at a temperature of about 140.6 kg / cm2 (2000 psi) at a flow rate of about 152.4 to 15 cm (five feet) per second.This feature greatly reduces the capital cost of the equipment and the system can be made portable.

In addition, the occlusion or plug flow of the reactants through the tubular coil results in improved mixing of the chemical reactants, as the curvature of the coil tends to cause a secondary flow in the liquid, tending to spirally on the inner surfaces of the coils, enhancing mixing with the gas phase. The arcuate nature of the helical tube Arc-25 causes a double spiral-shaped secondary flow into the liquid and the gas phase flows towards the "tip" of the coil, with gas inclusions or plugs being pulled through the bottom of the coil for thorough mixing. In addition, since the reaction vessel 30 formed by the tubular coil is much smaller in diameter than known reaction vessels operating in the same pressure and temperature ranges, the efficiency of the oxidation process is improved, since the reactants have little chance of bypassing the oxidation reaction and better stability of the reactants. minimizes the potential occurrence of environmental problems.

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The present invention also allows different temperature gradients to be applied to successive portions of a tubular helix along its entire length. In a divided embodiment in a container vessel, the temperature of this heat exchange fluid inside each compartment can be adjusted to fine tune the rate of reaction in each part of the tubular coil. In addition, when a heat exchange fluid is used, the level of the fluid in each compartment can be adjusted relative to the coil immersed in the fluid, which also affects the chemical reaction as a result of the external temperature gradient affecting the coil portion of each compartment.

The alternative tubular coil tubing structure allows the inflowing two-stage waste stream to pass through the inner tube and return as the inner flow of the ring between the inner tube ul-15 and the inner circumference of the concentric outer tube. This allows countercurrent heat exchange between the waste stream in the inner tube and the return stream in the outer tube, and thus the heat exchange fluid-20 in the tank may not be needed. This alternative structure is particularly well suited for the treatment of reactances at or near the autogenous site, where no heat supply or removal is required. The concentration of the reactants can be set in advance so that a certain amount of chemical reaction and heat release takes place as the waste steam passes through the inner tube. The chemical reaction continues as the reactances return along the ring between the tubes and the reaction heat heats any subsequent waste stream coming through the inner tube. 30 In addition, such a tubular structure allows for an ascending temperature reaction rate compared to a more phase-type reaction rate in a compartmentalized tank.

The use of a long tubular coil as a reaction vessel 35 allows multiple spraying or

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9 ‘^ the use of discharge points at several points along the entire length of the tubular coil and gas, liquid or solids can be removed at different points. Multiple spray sites allow the addition of fresh reactances when, for example, the reaction has heated the temperature of the waste stream. For example, the removal of gaseous or solid reaction products at intermediate points along the length of the tubular coil may allow the rate of waste flow to be reduced downstream of the outlet, thus increasing the precipitation time of the remaining reactants.

The tubular coil, about one mile long, acts as an excellent environmentally friendly reservoir for high pressure and temperature reaction flow, preventing such flow from escaping into the atmosphere. In addition, such a long tubular coil is very well suited for temperature control, enabling continuous heat supply, autogenous operation and continuous heat removal. The heat exchange fluid surrounding the tubular coil in the container may include vaporous, liquid or gaseous heat exchange fluids. In addition, the initial heat required for the reaction temperature can be suitably generated by direct steam injection inside the tubular coil. The tubular coil and in particular the nested tubular structure as well as the multiple spray points allow autogenous operation without the need for heat input or removal, as the temperature can be controlled by varying the concentration of reactants.

According to the present invention, there is provided a reaction apparatus comprising, in one embodiment, a conductor in the form of a meandering tubular helix provided with generally "oval" or "oval" portions or loops having substantially vertical sides. Such a generally oval helical or tortuous ribbon according to the present invention is placed so that most or all of its diameter is vertical. This means that the main axis of said oval or twisting ribbon is This shape of the reaction coil allows surprisingly good mass and heat transfer of the reactants, reduces pulping of the reactants in the reaction apparatus, improves mixing and provides optimal precipitation times for the liquid and vapor phases of the reaction mixture, as well as other advantages described in more detail below. The reaction system according to the invention is particularly well suited for use in the wet oxidation of municipal waste containing combustible material, but the method and apparatus according to the present invention can also be used in connection with other chemical reactions.

15 By making the coil or part thereof "oval" instead of circular, the descending part of a vertical reaction apparatus with a downhole is approached in more detail. In this vertical descending part, the least dense component, i.e. the steam phase, resists the downward flow of the liquid phase 20, thus allowing better mixing and contact of the reactants. This resistance of the vapor phase to the downward flow of liquid also increases the precipitation time of the liquid phase in the descending part. The increased mixing of the reac- dances and the increased precipitation time of the vapor phase ____ in the descending part result. greater mass transfer between oxygen and the oxidizable waste components for a more efficient wet oxidation reaction. The upwardly extending portions of the oval tubular helix 30 have additional advantages. The gaseous phase rises in these parts at a faster rate than the liquid, and the solid components move most slowly due to the effect of gravity. This results in better mixing and heat transfer, with the suspended solids "pulsating" in the rising parts under the action of gas bubbles.

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Tubular parts through which the flow of reactances usually takes place horizontally, i. It is believed that the flow pattern of the reactants through these generally horizontal portions reduces the efficiency of the system by causing larger deposits of liquid and vapor phases, thereby reducing mass transfer rates and causing the reactants to pulp as they pass through the system. the present invention further provides surprising improvements in the mass transfer properties and flow stability of the system.The term "oval" as used herein refers to the shape of a tubular reactor, whether the "ellipsoid" is closed or open, thus the tubular reaction vessel generally includes vertically extending side portions. which define the ascending and descending parts, as well as the generally horizontal parts, in which case the tubular shape can be tortuous or helical.

The conduit of the present invention, which forms a generally oval tubular helix, may comprise a simple tube or, alternatively, a generally concentric tube assembly having a hole in the center, i.e. an inflow channel, surrounded by an annular or outflow channel. In general, concentrically placed put-25 wedges have the added advantage that the wall of the inner tube can be relatively thin due to the small pressure difference between the tubes, which improves heat transfer. The "helical force" of the pipe ____ bends or arches contained in the device increases its resistance to internal pressures generated during waste treatment, which may exceed 140.6 kg / cm2 (2000 psi).

The curved parts of the reaction apparatus also cause a secondary flow in the reactances, which is believed to occur in the form of a "double helix". This secondary flow further mixes the reactants together, thus accelerating the 35 wet oxidation reactions. As stated above, the substantially vertical parts of the device form downward and upward inflow portions. The barrier and plug flow patterns desired in tubular reactions are achieved in these vertical inflow portions to a greater extent than in a device containing a coil.

This preferred embodiment of the present invention may also include a heat exchanger tank which partially or completely surrounds the oval reaction apparatus of the present invention. This container may also be divided by partitions into a series of chambers in which one or more loops of the reaction device are located. The tank can be filled with a heat exchanging medium, such as oil or water, to conduct heat to or from the divided reaction coil, or an oven can also be used. The heat can be introduced into the reaction coil by means of a heat exchange fluid during commissioning and then removed from the reaction coil after achieving a self-sustaining exothermic reaction.

In connection with the oval reaction coil or twisting tube of the present invention, a method is used in which a liquid containing a combustible material such as municipal waste is directed to flow through an oval coil or coiled tube reaction apparatus according to the present invention as an incoming waste stream; 25 sena. Available oxygen is added to the waste, for example in the form of air, oxygen-enriched gas or pure oxygen. The temperature and pressure of the oxidized effluent are raised to generate a self-sustaining exothermic oxidation reaction within the reaction apparatus. The reaction products 30 are directed to flow out of the reaction apparatus as a waste stream. The wet oxidation reaction is optimized to cause both a barrier and plug flow in the vertical ascending and descending portions and a secondary flow of reactances in the curved portions of the coil. The precipitation time of the steam step 35 increases in the substantially vertical descending parts of the helical reaction apparatus head i 13 '' ·> 7 '2. Pulping of reactances in the system is minimized by shortening the generally horizontal portions of the coil assembly and using predominantly vertical ascending and descending portions. The rotation ratio also increases considerably, so that both lower and higher transmission capacities can be achieved than in a reaction apparatus containing a helical coil.

The preferred "oval and meandering" embodiment of the present invention can be placed in a new or cracking unit so that the oval meandering tube extends around the furnace body and is heated, for example, by thermal radiation. The heating unit may include a preheater, such as a helical portion in the chimney, and the heater may be fueled by a gas, such as methane, generated by the waste by a separate reaction.

The concentrations of combustible material and oxygen, as well as the amount of heat added to or removed from the system, can be controlled to control the overall reaction of the waste, including the time required for complete oxidation of the waste and reaction temperatures at various lengths of the reaction coil. In the case of the concentric pipe assembly according to the present invention, the reaction can be monitored so that the reaction continues in the outflow channel or ring, which acts as a heat exchanger with the inflow channel to further heat the incoming waste stream.

Preferred embodiments of the method and device according to the invention appear from the dependent claims 2 to 6 and 8 to 11.

These and other advantages and features of the present invention will become more apparent from the following description with reference to the appended claims and the drawings, in which: - 7 ') 14' '' '* -

Figure 1 schematically shows a reaction system according to the present invention comprising a compartmentalized tank;

Figure 2 schematically shows a reaction system 5 according to the invention, comprising a helical structure formed by nested tubes;

Figure 3 is a partial perspective view of this helical structure formed by nested tubes;

Fig. 4 schematically shows a reaction system in which a pressurized heat exchange fluid is placed in a tank;

Fig. 5 schematically shows a reaction system equipped with pressure control to create a vapor pressure space above the heat exchange fluid in the tank vessel; Fig. 6 schematically shows the addition of a condenser or a ventilator to change the temperature between outflow and inflow;

Figure 7 schematically shows a reaction system including multiple spray or discharge points along the length of a put-20 coil;

Figure 8 schematically shows a reaction coil according to the present invention;

Figure 9 schematically shows a simple vertical helix of the present invention; Fig. 10 schematically shows a reaction system according to the present invention comprising a divided vessel;

Figure 11 shows a partial perspective view of a combination of concentric tubes according to the present invention;

Fig. 12 is a side view of a cross-section of a connector end of an embodiment of a combination of concentric tubes of the present invention;

Figure 13 schematically shows a reaction system of the present invention comprising concentric ones. a combination of tubes; i 15

Figure 14 schematically illustrates a reaction system according to the present invention that includes multiple locations along the length of a reaction helix for feeding and removing reactants and products; Figure 15 is a schematic side view of an oval serpentine embodiment of the present invention;

Fig. 16 is a schematic side view of a reaction system using an oval-shaped winding reaction vessel; Figure 17 shows a top view of the reaction system of Figure 16.

Figure 1 schematically illustrates an above ground reaction system 10 in accordance with the present invention. A waste feed stream, i.e., a first reactance, is passed through a passage 12, a heat exchanger 14, and a passage 16 to a long tubular coil 18 within a reservoir 20. If it is desired to use the reaction system 10 for the wet oxidation of a waste stream containing dilute or-20 organic waste, air or pure oxygen is sprayed into this waste stream through the duct 22.

As shown in Figure 1, the reservoir 20 is divided by partitions into a series of successive compartments filled with heat exchange fluid 24. The fluid 24 is pumped from the storage reservoir 26 via line 28 to individual compartments of the reservoir 20. By closing the valve 30 in the line 28 and opening the valves 43 and 34, the liquid 24 is directed to pass through the line 36 to the heat exchanger, where it is heated to an initial temperature which allows a reaction to take place in the waste stream in the tubular coil 18. The heated liquid 24 leaves the heat exchanger 38 via line 40 and returns to the tank 20 via line 28. Alternatively, it may be necessary to remove heat from the liquid 24 after the reaction has been piped; 7 2 in the earth helix 18 has become autogenous. In this case, the liquid 24 can be circulated through a heat exchanger placed in the line 44 to cool it to the desired temperature.

The level of liquid 24 in each compartment of the container 20 can be selectively monitored by using any of the valves 42 to drain liquid 24 through line 44 to storage tank 26. In addition, if liquid 24 reaches boiling temperature, pressurized steam 10 can be released from any pressure relief line 46 or steam can be recirculated to condenser 46 for the system.

Although the heat exchanger 24 shown in Figure 1 is a liquid, a gaseous or vaporous heat exchanger can also be used. When using a gaseous heat exchanger, a fan or blower is connected to the system at storage tank 26.

Once the waste stream has reacted in the tubular coil 18, it passes through line 48 to separator 50, where the steam outlet 20 exits through line 52 and the liquid outlet through line 54 to exchanger 14. As the liquid exits through exchanger 14, its temperature is also used to heat or cool the waste. the inlet flow.

·· '25 When treating dilute organic waste, the reaction system 10 pumps a liquid waste inlet stream to the tubular coil 18 at a pressure of about 84.37 to 140.6 kg / cm 2 (1200-2000 psi) along with a gas such as air or oxygen. , which is added via line 22. The gas and liquid flow rates are adjusted to cause a two-stage waste flow shut-off or compression flow through the tubular coil 18, whereby the reactants are thoroughly mixed. The reactants are heated in a coil 18 to a temperature which results in the disappointment of the waste stream ha-35, this temperature generally being between 149 17 ° C and 9 ° C.

- 316 ° C (300 - 600 "F). Thus, the reaction in the coil 18 takes place under the combined conditions of high pressure, high temperature and two-stage shut-off flow of the waste stream.

5 This system provides a thin-walled reaction vessel, i. the advantages of the tubular coil 18, this coil allowing, due to its length, the necessary precipitation time for the reactants in the reaction zone to achieve the desired amount of oxidation. For reaction 10, the required high temperature and pressure are contained in a thin-walled tubular coil, which is unexpected because these types of reactions are generally carried out in very thick-walled pressure vessels. This feature significantly reduces the cost of capital for the hardware. In addition, the closing or compression flow of the reactants through the tubular coil, i.e. the reaction vessel 18, improves the mixing of the chemical reactances because the curvature of the coil tends to cause a secondary flow in the liquid so that the liquid tends to flow along the spiral with the coil bases. In addition, since the reaction vessel formed by the tubular coil 18 is many times smaller in diameter than known reaction vessels operating in the same temperature and pressure ranges, the efficiency of the oxidation process is improved because the reactances have little chance of bypassing the oxidation reaction.

As can be understood from the liquid dynamics of the described reaction system, the simultaneous simultaneous flow of liquid, gas or solids sufficient to produce a barrier or compression flow is thoroughly mixed from its various components, which is important. in connection with chemical reactions such as wet oxidation. From low to medium velocities, the bubble background is followed by flotation flow. In the case of higher mass flows, the flows change into plug flows according to the brackets, ie :: - 2, respectively. In the most preferred method and apparatus of the present invention, the liquid and dissolved solids are separated by separate gas plugs, which causes back-mixing and provides a closer pulsating contact between the liquid and gas stages. In addition, plug flow occurs at a higher rate. A bend or curve in the pipe separates the steps. The bend can cause bubbles to coalesce to form plugs and separate the accompanying droplets in the annular flow. The curvature of the coil in the preferred embodiment also causes a secondary flow in the liquid in the form of a double spiral. As described above, the liquid is involved in the flow on the inner surface. The recommended horizontal helix in connection with the plug flow thus provides a thorough and close contact between the liquid and gas stages while allowing relatively high velocities.

As already mentioned above, the reaction coil 20 is preferably thin-walled. In previously known pressurized above-ground reaction vessels, the wall thickness of such a vessel is about 15.25 cm (six inches) to withstand changes in reaction pressure and vessel pressure. The diameter of the reaction vessel may be 18.3 to 3.05 m (6 to 10 25 feet) to make a series-type reaction commercially possible. For example, the tubular coil reaction vessel of this invention may be about two inches in diameter, including a flow of about 30.5 to 244 cm / s (1 to 8 feet / s) at a pressure of about 140.6 kg / cm 2 (2000 psi), and at 288 ° C (550 ° F). It will be appreciated that the diameter of the inner tube may be one inch or less up to about 15.25 cm (six inches) is recommended. : or plugs when the shut-off flow is maintained. TYY

in the case of a reaction, the gas phase constitutes about 35 to 30% by volume, the reaction temperature is about 260 to 316 ° C

f 'r: · 7 o 3.9 (500 - 600 ° F) and pressure about 140.6 kg / cm2 (2000 psi). The tubes are best made of a seamless nickel or titanium alloy. For example, a seamless nickel alloy tube may have an outer diameter of 6.03 cm (2.375 inches), an inner diameter of 4.57 cm (1.8 inches), and a wall thickness of 0.73 cm (0.287 inches). The plug flow is maintained in this tube at specified temperatures and pressures at a flow rate of about 45.7 to 244 cm / s (1.5 to 8 feet / second).

Referring again to Figure 1, the present invention provides for the application of various temperature gradients to successive portions of a tubular helix 18. Since the tank 20 is divided into compartments, the temperature of the heat exchange fluid 24 in each compartment can be adjusted up or down if desired. This allows fine adjustment of the reaction rate in each part of the tubular coil 15. In addition, the liquid 24 in each compartment can be adjusted to different levels with respect to the coil 18 immersed in the liquid, which also determines the rate of chemical reaction as a result of changes in the external temperature gradient 20 acting on the coil part in each compartment.

Figures 2 and 3 show an alternative nested tubular structure for a tubular coil 18 comprising two generally concentric tubes 56 and 58. To allow countercurrent flow of waste, the end of tube 56 (i.e., the right end of tube 25 56 as seen in Figure 2) is spaced inwardly from the end of tube 58. is closed. The inflowing biphasic waste stream passes through the inner tube 56 and returns within the ring formed between the outer circumference of the inner tube 56 and the inner circumference of the concentric, i.e., surrounding outer tube 30 58. This arrangement allows countercurrent heat exchange between the waste stream in line 56 and the return stream in line 58, making the heat exchange fluid 24 unnecessary. This arrangement is particularly well suited for the treatment of 35 reactants at or near the autogenous site 20 '2, where no heat supply or removal is required in the tank 20. For example, the concentration of reactants passing through the inner tube 56 can be adjusted in advance to a predetermined number of chemical reactions. the heat of reaction is generated during the time it takes for the waste stream to reach the end of pipe 56. This chemical reaction then continues as the reactances return inside the ring in tubes 56 and 58, thus allowing the heat of reaction in the return waste stream to be transferred through tube 56 to heat the waste stream. In addition, this nested tubular structure allows for an ascending reaction rate compared to the more step-like reaction rate caused by the compartmentalized tank-tia described in connection with Figure 1.

Referring to Figure 4, it also shows a container vessel 20 containing a tubular coil 18. The coil 18 is immersed in a heat exchange fluid 24 as above, but the fluid 24 is placed under pressure inside the reservoir 20. To begin the drive-20 process, the pump 60 supplies fluid 24 through line 62 to heater 64, with the liquid then returning via line 66 in a heated state to reservoir 20. Alternatively, a heating coil 68, jacket, or direct steam spray may be used to raise the temperature of the liquid 24:25. When the reaction system operates autogenously due to the heat generated by the reactants inside the tubular coil 18, it is not necessary to use the heater 64 or the heating coil 68. In fact, it can be. it is necessary to remove heat from the liquid 24 by closing the valves 70 and 75 and opening the valves 72 and 73, and by pumping the liquid 24 through the cooler 74 and returning the cooled liquid to the tank 20.

As shown in Figure 5, a pressure control valve 76 is used to control the top of the liquid 24 in the tank 20. The pressure of the steam space 78 on the 35 side. The reaction heat of the reactants in the tubular coil 21 causes the liquid 24 to boil, which increases the pressure of the vapor in the space 78 above it. When the pressure becomes too high, the valve 76 releases excess steam through line 80 to condenser 82 and condensed the liquid returns to the reservoir 20 via line 84.

Figure 6 shows the reaction system 10 further including a capacitor or exchanger 86 so that a temperature exchange occurs between the outgoing and incoming flow 10 via lines 48 and 16, respectively.

This allows a smaller steam treatment system to be used because the amount of water vapor in the steam outflow is reduced. Since the temperature of the liquid in the line 49 is also reduced, this considerably reduces the size and cost of the valve 87 of the separator 50, 15 and the heat exchanger 14.

As shown in Figure 7, the use of a long tubular coil 18 as a reaction vessel allows for the introduction of multiple reactance spray or discharge points along the length of the tubular coil. Gaseous, liquid 20 or solid reactants may be added at multiple points along the length of the tubular coil 18, such as at spray points 88 and 90. In addition, gas, liquid or solid components may be removed at various points, such as 92 and 94. Such multiple spray points allow, for example, fresh reactances to be added. the waste stream has been heated by the reaction, thus improving its overall reactivity and capacity. The removal of gaseous or solid reaction products at intermediate points along the length of the tubular helix allows, for example, a reduction of the waste flow rate from the outlet to the downstream, thus increasing the precipitation time of residual reactances.

The approximately 1.609 m (one mile) tubular coil provides an excellent reservoir for high pressure and temperature reaction flow to prevent escape into the atmosphere. Such a long tubular coil is also very suitable for temperature control, as described above, allowing continuous heat supply, autogenous operation and continuous heat removal 5. The liquid surrounding the tubular coil 18 in the tank 20 may contain vaporous, liquid or gaseous heat exchange fluids. by injecting steam directly into the helical coil 18 of the tubular 10. Such steam spraying can be performed prior to introducing reactances into the tubular coil 18. The tubular coil 18, and more specifically, the nested tubular structure of Figures 2-3, ai the multiple spray / discharge arrangement of Fig. 7, allows autogenic operation without the need to supply or remove heat, since the temperature can be controlled by varying the concentration of reactants.

Referring to Figure 8, there is shown schematically a "ring-like" reaction apparatus 120 according to another embodiment of the invention, including a conduit 122 forming a series of generally oval portions or loops 124, one of which is shown in Figure 9. Each loop 124 includes a substantially vertical ascending and a corresponding substantially vertical descending portion 128. Although the shape of each loop 124 is generally oval or pseudo-rectangular, it is preferred that portions 126 and 128 be substantially vertical to achieve the desired flow pattern and deposition times of the present invention. The oval shape 30 of each loop 124 further minimizes the horizontal flow of reactants by minimizing the length of the curved portions 130, with only two such curved portions being shown in Figure 9 for simplicity. As will be apparent in more detail from the description of the process of the present invention, the vertical ascending portion 23 «-72 126, the descending portion 128, and the curved portions 130 of the reactor coil 120 control the mixing of the reactances. The curved portions 130 also increase the structural integrity of the reaction coil 120 due to the bending strength of the loop.

The conduit 122 is preferably a tube having an inside diameter of about 0.9525 to 15.25 cm (0.375 to 6.0 inches), preferably 0.9525 to 5.08 cm (0.375 to 2 inches). The improved reaction efficiency of the present invention allows a larger amount of waste to be treated at a lower t-10. In some applications, it may be desirable to use a conduit 122 with an inner diameter outside of this preferred range. The walls of the conduit 122 are thinner than in a conventional tubular reaction apparatus due to the increased durability caused by the conduit 122 being helically formed. The walls of the conduit 122 may be about 0.0762 to 0.635 cm (0.03 to 0.025 inches) thick, depending on the exact nature of the reaction to be performed, the volume of the conduit 122, and the strength of the materials used to make the conduit 122. Suitable materials for wire 122 include stainless steel and certain titanium alloys. Other suitable materials for this purpose are also known to those skilled in the art. Seamless nickel or titanium alloy steels are particularly useful due to their excellent corrosion resistance.

It is important that the reaction coil 120 be oriented so that the major diameter or major axis of the oval is substantially vertical. The height "H" of each loop shown in Figure 9 is preferably about 152.5 to 610 cm (5 to 20 feet), especially 185 to 305 cm (6 to 10 feet). Experimental findings ... show that vertical sections less than 122 cm (four feet) in length have only a slight beneficial effect. Both the ascending portion 126 and the descending portion 128 comprise about 75 percent or more of the total height of each loop 124. This is necessary for a favorable

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to achieve a pattern, precipitation times, and pulping control in accordance with the present invention and to prevent drying of the downcomer 128. The curved portions 130 must be short enough to eliminate substantially horizontal flow without creating a sharp bend that would significantly reduce flow or cause blockage. Thus, the length of each curved portion 130 marked "L" in Figure 9 should preferably be less than about 60.1 cm (two feet). Other dimensions may be appropriately selected in strict accordance with the principles of the present invention.

The length of the line 122 is again determined by the type of reaction to be carried out and the reaction parameters such as heat and reaction time. For the treatment of municipal waste by the wet-15 oxidation method, the length of line 122 is preferably about 305 to 1830 m (1000 to 6000 feet). This ensures that a large amount of sludge can be substantially completely oxidized in the coil 122 at an acceptable rate of mixture flow. The number 20 of loops 124 forming the reaction coil 120 is determined by the dimensions of the loops 124 described above and the length of the conduit 122. Although the reaction coil 120 is intended for an above-ground reaction device and is thus a relatively easy to carry device, it may be advantageous to place the reaction coil 120 below the ground while, of course, maintaining the vertical direction of the loops 124.

Fig. 10 shows a reaction system 132 according to the present invention, in which, for example, a pressurized inlet waste stream containing diluted municipal waste is sprayed into a duct 134 and passed through a heating device 136, which may be operated by, for example, a gas or electric heater. The incoming waste stream is heated to a temperature of about '149 IC (300 eF), which greatly increases its rate of reaction with oxygen during wet oxidation. As the heated waste stream leaves the heating device: it is directed to flow through channel 138 to a reaction vessel 140 which, as described above, includes a vertical generally oval structure. It may be desirable to insulate the duct 138 to retain thermal energy.

As the heated waste liquid stream passes through channel 5 138, available oxygen is supplied therethrough via gas supply line 142. Oxygen acts as the second reactance in the wet oxidation system, with the combustible portions of the waste liquid stream forming the first reactance. The oxygen feed rate is generally controlled and thus reaction 10 can be controlled by increasing or decreasing the amount of oxygen fed to the waste stream. Air, pure oxygen, or oxygen-enriched gas can serve as suitable oxygen sources for this purpose. In some applications, it may be advisable to inject oxygen into the waste liquid 15 other than through the supply line 142 or at multiple injection points.

As shown in Figure 10, the reaction coil 140 is placed in a tank vessel 144 having a plurality of chambers, each such chamber containing a simple loop of the reaction coil 140. Other arrangements can be used by placing multiple loops in each compartment. In an alternative arrangement (not shown), the ascending portions of the reaction coil 140 are placed in the first set of compartments and the descending portions in the second compartment set. This increased reaction control may be desirable in some cases.

The reservoir 144 allows heat exchange between the fluid flow under the exothermic wet oxidation reaction and the reservoir 144 from the storage tank 148 through line 150 between the pump 30 heat exchanger 146. If desired, the heat exchanger 145 can be heated by closing the valve 152 and opening the valves 154 and 156, with the heat exchanger 146 passing through line 158 to heat exchanger 160 and then back to line 150 via line 162. 35 Alternatively, it may be necessary or desirable in some 26 r ί γι <-? η O 'J /! Ζ.

In some cases, the heat exchanger 146 removes the heat it receives from the reaction coil 140 during the exothermic wet oxidation reaction. This can be accomplished in a number of different ways in the present system, such as by reversing the flow of the heat exchanger 146 or by using a heat exchanger (not shown) in conjunction with the storage tank 148. The heat exchanger can be returned to the storage tank 148 via line 149.

The amount or level of heat exchanger 146 in the reservoir 144 can be adjusted via valves 164 included in this embodiment for selectively monitoring the level of heat exchanger 146 in each compartment of the reservoir. The pressure relief valves 166 are also in use and are shown placed on top of the container 144. The pressure relief valves 166 also allow for the removal of steam that may form if the heat exchanger 146 boils during operation. The heat exchanger 146 may contain a liquid, such as an oil, or a gaseous substance. In applications where the heat exchanger is 20 gas or steam, the storage tank 148 is provided with a fan or blower.

The diluted waste stream is preferably pumped to the reaction coil 140 at a pressure of about 105.5 to 154.7 kg / cm 2 (1500 to 2200 psi). As noted above, available oxygen is sprayed into the waste liquid through supply line 142. It is best to use pure oxygen or oxygen-enriched gas, although air is also suitable for use.

Increasing the oxygen content of the waste stream increases the rate of the wet oxidation reaction. As the wet oxidation reaction proceeds, the temperature of the waste stream 30 inside the coil 140 rises.. To about 260 to 371 ° C (500 to 700 ° F). At this temperature, the wet oxidation reaction is self-sustaining. the amount of combustible material and oxygen is available, the two reactances being in sufficient contact with each other, so that the heat i 27 r,; 7: 2 can be removed from the reaction coil 140 together with the heat exchanger 146. It may be desirable to use tank compartments. to add heat to the effluent as it first enters the reaction coil 140 and then removes heat near the end of the coil 140. The concentration of combustible waste, the concentration of oxygen added to the effluent, the flow pattern and velocity of the reactants in the reaction coil 140, and the temperature of the reactants aa is adjusted so that the waste is substantially completely reacted while leaving the reaction coil 140. It is also possible to perform the reaction "supercritically" at temperatures above 371 ° C (700 ° F) and pressures above 225 kg / cm 2 (3200 psi). Supercritical reactions may be desirable in certain applications of this invention, such as in the treatment of various tedious industrial wastes.

When the waste stream has reacted substantially completely in the reaction coil 140, the reaction products flow out of the reaction coil 140 through line 168 to separator 170. The reaction products, i.e., waste effluent, are then separated to form a liquid stream and a low volume sterile ash. The liquid stream at the still high temperature can be led to flow through line 172 to the heating device 136 for heating the inlet stream. The liquid stream can also be used to dilute the inflowing waste. The effluent of the wet oxidation reaction has mainly reduced oxygen demand.

- The generally oval shape of the reaction coil 140 contains, as described in more detail above, important advantages in treating the waste liquid by the wet oxidation waste reaction V. '30. When air or oxygen is sprayed into the waste liquid via the gas supply line 142, the flow of waste liquid and sprayed gas is controlled so that a plug or shutoff flow is achieved in the reaction coil 140, this flow being, as will be appreciated by those skilled in the art, the relative rates of vapor and liquid phases. A plug or shut-off flow is recommended because it achieves good mixing and thus improves the mass transfer of the reactants. Thus, better contact between oxygen and combustible material is achieved. In the context of the present invention, the plug or barrier flow and mass transfer provided by such a flow is further increased by the generally oval shape of the reaction coil 140.

Referring to Figures 8-10, as the gas or liquid mixture 10 passes through the ascending portion 126, the vertical position of this portion causes rapid movement of the gas phase. The curved portions 130 cause a double spiral secondary flow as a result of the movement of the mixture on the curved wall of the reaction coil. By minimizing the length of the 15 horizontal flow, the deposition of the phases that would otherwise occur is greatly reduced. It will be appreciated that as the liquid and vapor stages deposit to a greater extent on the reaction coil 140, less mass transfer between reactances is achieved. In addition to this improved mass transfer between reactants, less deposition of steps reduces pulping of the mixture as it passes through the reaction coil 140. Most importantly, the vapor phase, which is thinner in density than the liquid phase, "floats" in the liquid phase, thereby resisting the downward flow of the liquid phase 25 in the descending portion 128. This resistance greatly increases steam-liquid contact and mixing, thereby further increasing mass transfer and acceleration. In addition, the vertical position of the descending portion 128 of the reaction coil 140 increases the precipitation time of the steam step 30. As the steam rises, it stays in the descending part for a longer time. This leads to increased mass transfer and better utilization of the injected oxygen. Finally, making the descending portion 128 longer than 122 cm (four feet) in length prevents it from drying out, which would otherwise reduce the mass transfer area and also cause harmful spontaneous combustion. As described above, the ascending parts also improve mixing and heat transfer. The gas phase rises faster in the ascending parts than the liquid. As the effluent-5 stream contains solids, these dissolved solids move in the ascending portions at a slower rate due to gravity. Thus, three separate flow rates are created, which improves better mixing and heat transfer. Further, depending on the composition of the reactants 10, the dissolved solids "pulsate" in the ascending portions under the action of gas bubbles. This has been found to be particularly true when treating municipal sludge, with the liquid stream comprising dilute municipal sludge and oxygen or an oxygen-enriched gas.

Fig. 11 shows an alternative embodiment of a reaction coil formed by concentric tubes, in which the reaction coil 140 includes a concentric inner tube 174 inserted inside the outer tube 176. As indicated by the arrows, the waste inlet flows into the hole in the inner tube 174 and the wet oxidation reaction products flow downstream of the outer tube 176 through the ring formed by. Thus, in this arrangement, it can be seen that the outflow is heat exchange-25 relative to the inlet flow. The amount of heat transferred depends on the thermal conductivity of the material used to make the inner tube 174. Figure 12 shows a cross-section of reaction 140 opposite the arrow indicating the direction of flow of the reaction products as they exit the inner tube, "174 · 30, and enters the outer tube 176 to form a ring.

Fig. 13 schematically shows a waste reaction system according to the present invention including the concentric tube assembly shown in Figs. 11 and 12. Also in this case, the diluted waste liquid 35 is caused to flow through the channel 134 to the heating device 136, 30 r -. «7 ·. · /. L.

wherein the temperature of the waste liquid is raised to accelerate the wet oxidation reaction. As the heated waste liquid flows through the channel 138, oxygen or other oxygen-containing gas is fed to the waste liquid through the gas supply line 142 at a rate that increases the mass transfer inside the reaction coil 140 as described. The oxidized waste is then passed to a reaction coil 140 which, as mentioned above, in this embodiment of the invention comprises a combination of concentric nested tubes. In this context, the reaction coil 140 is shown only schematically to show the relative directions of the waste inlet flows and the outflow of the mainly reacted waste material. In reality, the reaction coil 140 has the same oval shape as shown in Figures 8-10. The wet oxidation reaction effluent is then directed to flow out of the reaction coil 140 via line 168. This effluent is again directed to separator 170 for clarification, thickening, dewatering, and the like.

Figure 14 shows a variation of the waste reaction system of the present invention including multiple spray or discharge points along the length of the reaction coil 140. Gaseous, liquid or solid reactants can be added at these multiple spray sites 178 and 180 to more closely control the wet oxidation reaction. Outlets 182 and 184 allow materials to be removed from the reaction coil 140 if desired. These multiple spray points allow the addition of fresh reactances for better utilization of the heat generated by the self-sustaining wet oxidation reaction. This means that unheated waste can be added directly to the reaction coil 140 at points where the reaction temperature is high. It should be noted that the heat 35 removed from the reaction coil 140 by the heat exchanger 146 can also be used to heat the incoming waste.

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31 in this application. The removal of reaction products at outlets 182 and 184 allows the rate of waste stream to be reduced from the outlets downstream, thus increasing the precipitation time of the remaining reactants.

Figure 15 shows a preferred "oval serpentine" of the reaction apparatus of the present invention. Reaction device 190 includes substantially vertical ascending and descending tubular portions 192 and interconnected generally horizontal tubular portions 194. The oval serpentine embodiment 190 is particularly suitable for furnace or cracking unit closed reaction systems, as shown in Figures 16 and 17.

The cracking unit shown somewhat schematically in Figures 16 and 17 includes a furnace body 196 having a smoke-15 barrel 198. The body 196 may be made of conventional furnace materials, such as steel-reinforced furnace bricks. An embodiment of this reaction system includes a preheating portion in the chimney 198, i.e., a circular coil 200. The waste liquid, which may comprise solids 20 dissolved in the liquid, is fed through an inlet line 202. As described above, the method of this system generally includes two reactants, such as dilute municipal slurry and oxygen, although the method and apparatus of this invention may also be used to treat a single "reactance". As described above, a gaseous reactance, such as oxygen or an oxygen-containing gas, may be added to the waste liquid in the inlet line 202 or to the reaction stream.

As will be appreciated from the following description, heated air is discharged through the chimney 198 in furnace 196 by preheating the reactants in coil 200. The preheated reactants are then fed through line 204 to an oval serpentine reactor section 190 at the bottom of furnace 196. As shown in the figure, this meandering tube 35 extends twice around the furnace body and the vertically extending portions 192 are stepped in a horizontal direction as shown in Fig. 16 so that both portions are schematically exposed to the radiant heater shown at 206. The radiation heater 206 may be a conventional burner, such as a methane burner. Methane can be generated by treating the effluent in an aerobic polishing unit. The treated waste material is then removed from the reaction apparatus via an outlet line 208. As will be appreciated, the recommended temperature at which the reactants are heated within the tubular system depends on the reaction itself. As described above, the waste is preferably heated to a temperature of about 204 to 316 ° C (400 to 600 ° F). The dimensions of the oval serpentine tube 190 may be the same as in the helical application described above. Thus, the length of the vertical portions 15 may be 152.5 to 122 cm (5 to 20 feet) or preferably about 183 to 304.8 cm (6 to 10 feet), while the length of the horizontal portions may be less than 60.86 cm (2 feet). ). As will be appreciated, the length of the reaction vessel containing the vertical ascending and descending portions, and generally the horizontal interconnecting end portions, depends on the reaction carried out in the reaction apparatus. For most applications, the length of the reaction device should be at least 305 m (1000 ft). However, when treating municipal sludge, the length of the reaction device should be at least 1219 to 1524 m (4000 to 5000 ft).

In connection with the present invention described above, several variations can, of course, be made within the scope of the appended claims.

Claims (11)

A process for conducting chemical reactions, wherein process reagents are passed through a tube (18) at a predetermined rate and at a predetermined temperature to effect a chemical reaction, to convert the reagents into one or more products, wherein the temperature is controlled by means of a heat exchanger medium (24) where the reaction tube is arranged, characterized in that a) a first reagent is led into a long tube-like coil (18) with thin walls under a predetermined pressure, the tube-like coil being arranged horizontally in the a vessel (20) filled with the heat exchanger medium (24) in direct contact with the coil; b) a second reagent is introduced into the tube-like coil (18) at a predetermined pressure; c) the feed and flow rate of the reagents. and their relative volumes are controlled at the predetermined pressure to achieve a two-stage plug and dust flow of the reagents through the and (d) the temperature of the liquid stream in the tubular coil (18) is controlled by means of the heat exchanger medium (24) to increase the temperature where the liquid stream temperature is lower than the predetermined, and to dissipate heat thereof. the temperature of the liquid stream is higher than the predetermined, in order to initiate in the liquid stream a chemical reaction which leads to heated liquid and reaction products. Process according to claim 1, wherein the chemical reaction is exothermic, characterized in that the heat exchanger medium (24) is heated to start the exothermic chemical reaction of the reagents in the tube-like coil (18) whose walls are thin and 38 away from the heat exchanger medium where said reaction becomes autogenous. 3. Process according to claim 2, characterized in that one of the reagents is a gas and the other is a liquid. 4. A process according to claim 1, characterized in that the reagents are introduced into the tube-like coil (18) comprising several substantially elliptical loops, each loop having a substantially vertically rising portion (126). and a substantially vertical descending portion (128). 5. A process according to claim 1, characterized in that the reagents are heated by heating devices as they are led into the tube-like coil. 15 One (18). 6. A process according to claim 1, characterized in that the reagents are introduced into a tube-like coil (18) which has an inner tube (56) arranged concentrically in relation to an outer tube 20 (58). the inner tube (56) is disposed within the outer tube (58), the reagents passing through the inner tube (56) in a first direction and the reaction product being returned in a second opposite direction through an annular space between the inner tube (56) and the outer tube (58). Device for carrying out chemical reactions, in which device reagents are passed through a tube (18) at a predetermined rate and at a predetermined temperature to effect a chemical reaction, to convert the reagents into one or more products. , and in which device a reaction tube is arranged in a heat exchanger medium (24), characterized in that the device comprises a long tube-like coil (18) with thin walls arranged horizontally in a vessel (20) to which a coil is arranged. A liquid stream comprising reagents is conducted at a selected flow rate to effect a plug or dust flow through the tube-like coil (18), one arranged in the vessel (20) and in direct contact with the tube-like the coil being heat exchanger medium (24) to control the temperature of the liquid in the coil (18), to supply heat where the temperature of the liquid stream is below a predetermined temperature and to be removed. when the temperature of the liquid stream exceeds a predetermined temperature, to initiate in the liquid stream a chemical reaction leading to heated liquid and reaction products, and means (44, 48) to receive the heated liquid and the effluent reaction products. -15 similar to the coil (18). 8. Apparatus according to claim 7, characterized in that several drainage points (182, 184) are arranged along the length of the tube-like coil to remove gas or solid particles from the liquid stream via one or more drainage points. Device according to claim 7, characterized in that the vessel (20) comprises a set of sections (144) for dividing the tubular coil (18) into parts, and means (38) for regulating the temperature 25 the flow of liquid in each of the parts of the pipe-like coil (18), to apply different temperature gradients in the pipe-like coil (18) one after the other, arranged along its length. 10. Apparatus according to claim 7, characterized in that the tube-like coil (18) comprises an inner tube (56) arranged concentrically in relation to an outer tube (58), such that the inner tube (56) ) is disposed within the outer tube (58), the inwardly flowing liquid stream being passed through the inner tube (56) in a first direction and returned in a second 40 --- 1 opposite direction via an annular space between the inner tube (56). ) and the outer tube (58), wherein the concentration of the liquid stream is regulated so that an exothermic reaction arises as the liquid stream flows in the first direction, which continues as the liquid stream flows in the second direction, the heat generated by the chemical reaction. where the liquid stream flows in the second direction, tili is used to heat the liquid stream flowing in the first direction. 11. Apparatus according to claim 7, characterized in that the tubular coil (18) has a plurality of substantially elliptical loops, each loop comprising a substantially vertical rising portion (126) and a substantially vertical descending portion (128).